Equilibrium cell potential

The change in the concentration of H3O+ is monitored with a pH ion-selective electrode, for which the cell potential is given by equation 11.9. The relationship between the concentration of H3O+ and CO2 is given by rearranging the equilibrium constant expression for reaction 11.10 thus... 

Temperature, K Enthalpy of reaction (AH ), kj/mol Free energy of reaction (AG ), kJ/mol Equilibrium cell potential (E ), V... 

The three values of ° are easily calculated from half-cell potentials. Then, we can predict with confidence that reaction (65) will not occur to an appreciable extent if solid copper is immersed in dilute acid. The negative value of ° (—0.34 volt) indicates that equilibrium in (65) strongly favors the reactants, not the products. 

The complete reaction may be regarded as composed of two oxidation-reduction electrodes, a Ox, a Red, and frOx , b Red, combined together into a cell at equilibrium, the potentials of both electrodes are the same ... 

Figure 1. Sketch of an electrochemical cell whose equilibrium (open circuit) potential difference is AE. (a) Conventional configuration and (b) short-circuited configuration with an air gap. M and R are the electrodes, S is the solvent (electrolyte solution). Cu indicates the cables connecting the two electrodes to a measuring instrument (or to each other).

As a reaction proceeds toward equilibrium, the concentrations of its reactants and products change and AG approaches zero. Therefore, as reactants are consumed in a working electrochemical cell, the cell potential also decreases until finally it reaches zero. A dead battery is one in which the cell reaction has reached equilibrium. At equilibrium, a cell generates zero potential difference across its electrodes and the reaction can no longer do work. To describe this behavior quantitatively, we need to find how the cell emf varies with the concentrations of species in the cell. 

If the equilibrium half-cell potentials for two redox reactions are different, electrons will be transferred from the reduced species in the... 

The Gibbs free energy for the reaction is related to the equilibrium cell potential ( 0) (Equation 6.4). For the reaction between hydrogen and oxygen to produce water, n, the number of electrons per molecule participating in the electrochemical reaction is 2 and AG has a value of —37.2 kJ mol giving Eq a value of 1.23 V... 

C19-0039. Write a paragraph explaining the linkages among cell potential, free energy, and the equilibrium constant. 

Potentiometric methods are based on the measurement of the potential of an electrochemical cell consisting of two electrodes immersed in a solution. Since the cell potential is measured under the condition of zero cmrent, usually with a pH/mV meter, potentiometry is an equilibrium method. One electrode, the indicator electrode, is chosen to respond to a particular species in solution whose activity or concentration is to be measured. The other electrode is a reference electrode whose half-cell potential is invariant. 

The latter does not yield a completely reproducible potential equilibrium is established after about two days. Nonetheless, it is often used in research on technically important galvanic cells working in alkaline media. 

Calculation of the internal cell potential is a very complicated matter because the electrochemistry of all of the species within the protocell would have to be balanced subject to their composition quotient Q, after which the standard free energy would have to be established from tabulations. The transport of Na+ would also change this balance, along with the ionic strength of the solution and the stability of the proteins or prebiotic molecules within the protocell. Such non-equilibrium thermodynamics forms the basis of the protocell metabolism. The construction... 

Experiments involving the Nernst equation are primarily concerned with concentrations. One or more of the concentrations in the Q portion of the Nernst equation are calculated by measuring the nonstandard cell potential and comparing this to the standard cell potential. Remember, you calculate the concentration from a measured voltage. Once the concentration is determined, it may be combined with other concentrations and used to calculate an equilibrium constant. 

The standard cell potential can also be used to calculate the equilibrium constant for a nE°... 

Note that we had to multiply the cell potential by — 1 because the net equilibrium 16.15 does not follow the accepted convention, that is, the SHE is not the anode. Equation 16.16 becomes... 

Useful work (electrical energy) is obtained from a fuel cell only when a reasonable current is drawn, but the actual cell potential is decreased from its equilibrium potential because of irreversible losses as shown in Figure 2-2". Several sources contribute to irreversible losses in a practical fuel cell. The losses, which are often called polarization, overpotential, or overvoltage (ri), originate primarily from three sources (1) activation polarization (r act), (2) ohmic polarization (rjohm), and (3) concentration polarization (ricoiic)- These losses result in a cell voltage (V) for a fuel cell that is less than its ideal potential, E (V = E - Losses). 

Table 6-4 Equilibrium Composition of Fuel Gas and Reversible Cell Potential as a...

A third calculation of a" gives 0.029874, which is substantially the same as the result of the second approximation hence, it can be used in Equation (20.27). As with the iterative procedure for calculating equilibrium constants from data on cell potentials, the iterative procedure for conductance data can be programmed for a computer. 

The galvanic cell pictured in Figure 7.1 is not at equilibrium. If switch S is closed, electrons will spontaneously flow from the zinc (anode) to the copper (cathode) electrode. This flow will continue imtil the reactants and products attain their equilibrium concentrations. If switch S is opened before the cell reaches equilibrium, the electron flow will be interrupted. The voltmeter would register a positive voltage, which is a measure of the degree to which the redox reaction drives electrons from the anode to the cathode. Since this voltage is a type of energy that has the potential to do work, it is referred to as a redox potential or cell potential, denoted as... 

Cell potential (E ) A measure of how far a redox reaction is from equilibrium. It is reported in units of volts. The higher the E, the greater the driving force for reaction. 

Here, we have substituted E, the standard potential for oxidation of H2, for —2FAG°, where AG° is the free energy change for reaction under standard conditions. Obviously, similar relationships can be written to calculate the equilibrium potentials for other fuels. For example, for alkanes, C, Azn z, the analogous relationship between partial pressures and the equilibrium cell potential is the following... 

The cell potential is simply the work that can be accomplished by the electrons produced in the SOFC, and this potential decreases from the equilibrium value due to losses in the electrodes and the electrolyte. For YSZ electrolytes, the losses are purely ohmic and are equal to the product of the current and the electrolyte resistance. Within the electrodes, the losses are more complex. While there can be an ohmic component, most of the losses are associated with diffusion (both of gas-phase molecules to the TPB and of ions within the electrode) and slow surface kinetics. For example, concentration gradients for either O2 (in the cathode) or H2 (in the anode) can change the concentrations at the electrolyte interface,which in turn establish the cell potential. Similarly, slow surface kinetics could result in the surface at the electrolyte interface not being in equilibrium with the gas phase. 

A cell whose equilibrium potential difference is affected by outer potentials is depicted in the scheme... 

Galvanostatic Transient Technique. In the galvanostatic method a constant-current pulse is applied to the cell at equilibrium state and the resulting variation of the potential with time is recorded. The total galvanostatic current ig is accounted for (1) by the double-layer charging, /ji, and (2) by the electrode reaction (charge transfer), i. ... 

Fig. 3.15 Energy diagram of semiconductor-metal photoelectrolysis cell, (a) No contact and no chemical potential equilibrium (b) galvanic contact in dark (c) effect of light illumination (d) effect of light illumination with bias, (e) Light illumination without bias, however in this case the semiconductor band edges straddle the redox potential for water photoelectrolysis.

Polarization. The net current flow produced in a cell results in a deviation of each half-cell potential from the equilibrium value listed in Table 3.3. This deviation from equilibrium is termed polarization, the magnitude of which is given the lowercase greek symbol eta, q and is called the overpotential, E-E°. There are two primary types of polarization activation polarization and concentration polarization. 

Ozkaya (76) studied conceptual difficulties experienced by prospective teachers in a number of electrochemical concepts, namely half-cell potential, cell potential, and chemical and electrochemical equilibrium in galvanic cells. The study identified common misconceptions among student teachers from different countries and different levels of electrochemistry. Misconceptions were also identified in relation to chemical equilibrium, electrochemical equilibrium, and the instrumental requirements for die measurement of cell potentials. Learning difficulties were attributed mainly to failure of students to acquire adequate conceptual understanding, and the insufficient explanation of the relevant... 

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